CN106120021A - A kind of polyester fiber with antibacterial, deodorizing and health care functions and its preparation method - Google Patents

Abstract

The invention discloses a polyester fiber with antibacterial, deodorizing and health-care functions and a preparation method thereof, belonging to the field of polyester fibers. The polyester fiber is of a skin-core structure, the polyester forms a core layer of the skin-core structure, and the polyvinyl alcohol-ethylene copolymer is arranged at the periphery of the core layer and surrounds the core layer to form a skin layer of the skin-core structure; the polyvinyl alcohol-ethylene copolymer is outwards connected with dimethylaminoethyl methacrylate along the radial direction of the skin-core structure, the dimethylaminoethyl methacrylate and divalent copper ions are complexed to form an antibacterial layer of the polyester fiber, and the tail end of the dimethylaminoethyl methacrylate is connected with polyethylene glycol to form a skin-friendly and hydrophilic layer on the surface of the polyester fiber. The polyester fiber has good antibacterial and deodorizing ability and heat-insulating ability, and has health promotion effects of promoting human body microcirculation, diminishing inflammation, relieving pain, accelerating wound healing, activating matrix, promoting in vivo waste discharge, relieving fatigue, regulating nerve, etc.

Description

A kind of polyester fiber with antibacterial, deodorizing and health care functions and its preparation method

technical field

The invention belongs to the field of polyester fibers, and in particular relates to a polyester fiber with antibacterial, deodorizing and health-care functions and a preparation method thereof.

Background technique

Because of its porous shape and chemical structure of polymers, textile fibers are conducive to the attachment of microorganisms. At the same time, in the process of wearing the human body, they will be stained with sweat, sebum and other human secretions and environmental pollutants. Microorganisms provide a source of nutrition. Therefore, the research and development of antibacterial function of textiles is of great significance. The fibers with antibacterial and deodorizing functions are all added antibacterial and deodorant drugs during the preparation process. After wearing or washing for a long time, the drugs are easy to fall off and become invalid. Moreover, most of the functional fibers only have a single function, and do not achieve perfect compounding of multiple functions. In order to improve the adaptability of edible products to the market, it is necessary to develop composite fibers with antibacterial, deodorant and health care functions.

Contents of the invention

The purpose of the present invention is to disclose a polyester fiber with antibacterial, deodorant and health care functions and a preparation method thereof. Accelerates wound healing, activates matrix, promotes waste discharge in the body, eliminates fatigue, regulates nerves and other health care effects.

A kind of polyester fiber with antibacterial, deodorizing and health care functions designed by the present invention, the polyester fiber is a skin-core structure, and the polyester constitutes the core layer of the skin-core structure, and the polyvinyl alcohol-ethylene copolymer is on the periphery of the core layer, Enclosing the skin layer forming the skin-core structure; the polyvinyl alcohol-ethylene copolymer is connected with polydimethylaminoethyl methacrylate outward along the radial direction of the skin-core structure, and the polydimethylaminoethyl methacrylate The ester is complexed with divalent copper ions to form an antibacterial layer of polyester fiber, and the end of polydimethylaminoethyl methacrylate is connected with polyethylene glycol to form a skin-friendly and hydrophilic layer on the surface of polyester fiber.

Further, the zirconium dioxide nanoparticles are embedded in the polyester core layer of the polyester fiber, and the mass of the zirconium dioxide nanoparticles is 1.5-4.0% of the mass of the polyester core layer.

Still further, the average particle size of the zirconia nanoparticles is 30-60 nm.

Furthermore, the thickness of the polyvinyl alcohol-ethylene copolymer skin layer of the polyester fiber is 7-15 μm, and the polyvinyl alcohol-ethylene copolymer skin layer contains several holes with a pore diameter of 20-50 nm and a porosity of 40 ~50%.

Furthermore, the polyester core layer of the polyester fiber is polyethylene terephthalate, and the average diameter of the polyester core layer is 14-20 μm.

Furthermore, the polydimethylaminoethyl methacrylate complexes with divalent copper ions through coordination bonds, and the molar ratio of dimethylaminoethyl methacrylate to divalent copper ions is 2 to 3:1 .

Furthermore, the polyethylene glycol has a molecular weight of 3.0-5.0 kDa, and the polydimethylaminoethyl methacrylate has a molecular weight of 8.0-10.0 kDa.

The present invention also provides a kind of preparation method of polyester fiber, comprises the steps:

1) Blend zirconia nanoparticles and polyethylene terephthalate to form mixed system I, sodium chloride and polyvinyl alcohol-ethylene copolymer to form mixed system II, then mix mixed system I and mixed System II is melt-blended, and the polyester fiber with the skin-core structure is prepared by the skin-core spinning method, and the skin layer in the polyester fiber with the skin-core structure is a polyvinyl alcohol-ethylene copolymer layer containing sodium chloride. The core layer in the polyester fiber of the core structure is a core layer containing zirconia nanoparticles, and the sodium chloride is sodium chloride with a nanometer particle size;

2) placing the polyester fiber with a sheath-core structure prepared in step 1) into water for immersion, washing, and dissolving sodium chloride crystals to obtain a sheath-core fiber with several holes in the polyvinyl alcohol-ethylene copolymer skin layer;

3) immersing the sheath-core fiber prepared in step 2) in bromoisobutyryl bromide solution, a free radical activation reaction occurs, and the fiber is fully washed to obtain a fiber with atom transfer radical polymerization initiating activity;

4) The fiber with atom transfer radical polymerization initiating activity prepared in step 3) is immersed in a dimethylaminoethyl methacrylate solution containing cuprous bromide and bispyridine under a nitrogen protective atmosphere to generate Polymerization to obtain polyester fibers functionalized with N,N-dimethylaminoethyl methacrylate;

5) The poly(N,N-dimethylaminoethyl methacrylate) functionalized polyester fiber prepared in step 4) undergoes a nucleophilic substitution reaction with potassium salt of polyethylene glycol under the condition of a phase transfer catalyst, A polyester fiber functionalized with poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate at the end is obtained.

6) Immersing the polyester fiber functionalized with poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate at the end prepared in step 5) in a divalent copper ion solution for a complex reaction to obtain Polyester fiber with antibacterial and deodorant health functions.

Further, the reaction time in the step 3) is 30-60 minutes, and the reaction condition in the step 4) is to gradually raise the temperature to 65-80° C., and then keep the temperature for 16-20 hours.

Further, the phase transfer catalyst in the step 5) is tetrabutylammonium bromide, the concentration of the divalent copper ion solution in the step 6) is 0.45～0.55mol/ml, and the complex reaction time is 1 ~2h.

As a technical preference of the present invention, the polyethylene glycol preferably has a molecular weight of 4.0 kDa.

As a technical preference of the present invention, the particle size of the zirconia nanoparticles is preferably 50 nm, and the mass percentage is 2.0-3.5%.

The principle of the polyester fiber prepared by the present invention:

The polyester fiber is designed into a sheath-core structure, in which the cortex is rich in pores to achieve the purpose of deodorization. The core layer is embedded with ZrO ₂ (zirconia) nanoparticles, which have the functions of heat preservation and health care, and the surface of the cortex is also bonded with two Copper ions (Cu ²⁺ ) are complexed to form an antibacterial layer, and polyethylene glycol is also introduced to improve the wearing comfort of polyester fibers.

The beneficial effects of the present invention are:

1. In addition to the heat preservation effect, the polyester fiber also has health effects such as promoting human microcirculation, anti-inflammatory and analgesic, accelerating wound healing, activating the matrix, promoting waste discharge in the body, eliminating fatigue, and regulating nerves; in addition, it can also deodorize and antibacterial , so it is a polyester fiber with multiple functions at the same time.

2. The preparation method of the polyester fiber is feasible, and can simultaneously prepare products with multiple functions. The operation is simple and feasible, and the cost is low, so it has a good application prospect.

Description of drawings

Fig. 1 is the fiber sectional view of the antibacterial and deodorizing health care function polyester fiber of the embodiment of the present invention;

Fig. 2 is the fiber sectional view of Fig. 1;

Among them, the labels in the figure are as follows:

1—polyvinyl alcohol-polyethylene copolymer skin layer, 2—porous structure in polyvinyl alcohol-polyethylene copolymer skin layer, 3—polyester core layer, 4—antibacterial layer, 5—hydrophilic, skin-friendly layer, 6 - ZrO ₂ nanoparticles.

detailed description

The following describes in detail the preferred embodiments of the present invention with reference to the accompanying drawings, so that the features and advantages of the present invention can be more easily accepted by those skilled in the art, and the protection scope of the present invention can be defined more clearly.

Example 1

As shown in Figure 1, the polyester fiber with antibacterial, deodorant and health care functions disclosed by the present invention is a skin-core structure, and polyester constitutes the core layer in the skin-core structure, becoming a polyester core layer 3, and the average weight of the polyester core 3 The diameter is preferably 14 μm (the diameter of the polyester core layer is controlled between 14 and 20 μm), and the polyester core layer with an appropriate diameter can be better connected with the polymer; the polyester in this embodiment is preferably polyethylene terephthalic acid Ethylene glycol ester, with ZrO ₂ nanoparticles embedded in the polyethylene terephthalate core layer 6, because ZrO ₂ nanoparticles, as a far-infrared material, not only has the effect of heat preservation, but also has the functions of promoting human microcirculation, anti-inflammatory Analgesia, accelerate wound healing, activate matrix, promote waste discharge in the body, eliminate fatigue, regulate nerves and other health effects. Simultaneously, in the present embodiment, the particle diameter of ZrO2 nanoparticle is 50nm, and content is ₂ % (the content of ZrO2 nanoparticle is preferably controlled between _2.0 ～3.5% ₎ , if ZrO2 nanoparticle content is too high will be Affect the strength of fiber, if it is too low, it will make the heat preservation and health care ability worse.

Combining with Figure 1 again, it can be seen that the polyvinyl alcohol-ethylene copolymer surrounds the skin layer forming the skin-core structure on the periphery of the polyester core layer, and becomes the polyvinyl alcohol-ethylene copolymer skin layer 1, and in this implementation, the polyvinyl alcohol-ethylene copolymer The thickness of the ethylene copolymer skin 1 is 9 μm (the thickness of the polyvinyl alcohol-ethylene copolymer skin layer can be controlled between 7 and 15 μm), and at the same time, in order to ensure the adsorption effect, the polyvinyl alcohol-ethylene copolymer skin layer has a porous structure , as shown in the porous structure 2 in the polyvinyl alcohol-ethylene copolymer skin layer in Figure 1, the porosity reaches 40-50%, and the pore diameter is 20-50nm, because too low porosity causes the adsorption capacity of odor molecules to be insufficient , and too high porosity will affect the mechanical properties of the polyvinyl alcohol-ethylene copolymer skin layer, and affect the graft density of the antibacterial layer of the complex formed by polydimethylaminoethyl methacrylate and Cu ²⁺ in the later stage, and finally It will affect the antibacterial ability of the fiber. Therefore, in this implementation, the polyvinyl alcohol-ethylene copolymer skin layer with a porous structure can have excellent adsorption capacity for odor molecules such as hydrogen sulfide and mercaptans produced in the metabolic process of the human body, and significantly reduce the odor caused by odor molecules. Adverse reactions to the central nervous system, oral cavity, throat and stomach irritation.

In conjunction with Fig. 1 and Fig. 2, it can be seen that polydimethylaminoethyl methacrylate is connected outwards along the radial direction of the sheath-core structure in the polyvinyl alcohol-ethylene copolymer, and the molecular weight of polydimethylaminoethyl methacrylate is In this example, it is 9.0kDa (the molecular weight of polydimethylaminoethyl methacrylate is controlled between 8.0 and 10.0kDa), and polydimethylaminoethyl methacrylate is complexed with Cu ²⁺ to form Complex, which constitutes the antibacterial layer 4 of polyester fiber, Cu ²⁺ is firmly bound to polyester fiber through coordination bonds, exerting durable antibacterial ability, and polydimethylaminoethyl methacrylate also has excellent antibacterial Ability, synergistic antibacterial properties with Cu ²⁺ can significantly improve the antibacterial properties of polyester fibers; the molar ratio of dimethylaminoethyl methacrylate to Cu ²⁺ is preferably 2 to 3:1, if dimethylaminoethyl methacrylate If the content of ethyl ester is low, the binding force between dimethylaminoethyl methacrylate and Cu ²⁺ will not be strong, which will affect the durability of antibacterial; if the content of Cu ²⁺ is low, it will affect the complex. antibacterial ability. The polydimethylaminoethyl methacrylate in the polyester fiber antibacterial layer prepared in this implementation has a strong binding ability to Cu ²⁺ . After 30 times of washing, Cu ²⁺ antibacterial ions are almost not lost, and still maintain a good Excellent antibacterial performance, the bacteriostatic rate can still be maintained above 86%.

In combination with Fig. 1 and Fig. 2 again, it can be seen that polyethylene glycol is connected to the end of polydimethylaminoethyl methacrylate, and the molecular weight of polyethylene glycol in this implementation is preferably 4.0kDa, and the affinity of polyethylene glycol Water can improve the skin-friendly property of polyester fiber, therefore forms hydrophilic, skin-friendly layer on the surface of polyester fiber, as shown in the hydrophilic, husband-in-law layer 5 among Fig. 1 and Fig. 2, after forming hydrophilic, At the same time as the skin-friendly layer, it can also endow the polyester fiber with a certain antibacterial electrostatic ability, so it effectively improves the wearing comfort in practicality, and endows the polyester fiber with a certain antistatic ability.

Therefore, the polyester fiber of this embodiment has multiple functions.

Example 2

This embodiment discloses the preparation method of this polyester fiber, comprises the following steps:

₁ ) The ZrO2 nanoparticles with a particle size of 30nm and the polyethylene terephthalate with a molecular weight of _8.0kDa are blended to form a mixed system I, and the quality of the ZrO2 nanoparticles is the _ZrO2 nanoparticles and polyethylene terephthalate 2.0% of the total mass of ethylene glycol diformate, nano-particle size sodium chloride and polyvinyl alcohol-ethylene copolymer with a molecular weight of 3.0kDa are melt blended to form mixed system II, and then mixed system I and mixed system II are melt-blended Mixed, through the composite fiber spinning method, the polyester fiber of the sheath-core structure is prepared, and the skin layer in the polyester fiber of the sheath-core structure is a polyvinyl alcohol-ethylene copolymer layer containing sodium chloride, and the polyester fiber of the sheath-core structure The core layer in the fiber is a core layer containing ZrO2 nanoparticles _;

2) Put the polyester fiber with a sheath-core structure prepared in step 1) into water for immersion and washing, and dissolve sodium chloride crystals to obtain a sheath-core fiber with several holes in the polyvinyl alcohol-ethylene copolymer skin layer, and the pore diameter is 20-30nm, porosity 45%, polyvinyl alcohol-ethylene copolymer skin thickness of about 9μm;

3) immersing the sheath-core fiber prepared in step 2) in a bromoisobutyryl bromide solution, and after reacting for 40 minutes, fully washing the fiber to obtain a fiber with atom transfer radical polymerization initiating activity;

4) The fiber with atom transfer radical polymerization initiating activity prepared in step 3) is immersed in a dimethylaminoethyl methacrylate solution containing cuprous bromide and bispyridine under a nitrogen protective atmosphere, and The molar ratio of cuprous bromide to dimethylaminoethyl methacrylate is 2:1, and the temperature is gradually raised to 65°C, and the reaction is kept for 18 hours to obtain poly(N,N-dimethylaminoethyl methacrylate) functionalized Polyester;

5) the polymethacrylic N, N-dimethylaminoethyl ester functionalized polyester fiber prepared in step 4) is mixed with polyethylene glycol under the catalysis of the phase transfer catalyst tetrabutylammonium bromide The potassium salt undergoes a nucleophilic substitution reaction to obtain a polyester fiber functionalized with poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate at the end.

6) Immerse the poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate functionalized polyester fiber with polyethylene glycol at the end prepared in step 5) in a divalent copper ion solution with a concentration of 0.5mol/ml Complexation reaction occurred in the reaction for 1.5h, and the polyester fiber with antibacterial, deodorizing and health-care functions was obtained.

The thickness of the polyvinyl alcohol-ethylene copolymer skin layer of the prepared polyester fiber is 9 μm, the pore diameter is 20-30 nm, and the porosity is 45%; the average diameter of the polyester core layer is 18 μm.

Example 3

The preparation method of the polyester fiber in the present embodiment, comprises the steps:

₁ ) The ZrO2 nanoparticles with a particle diameter of 50nm and the polyethylene terephthalate with a molecular weight of 10kDa are blended to form a mixed system I, and the quality of the ZrO2 nanoparticles is _equal to the _ZrO2 nanoparticles and polyethylene terephthalate 3.5% of the total mass of ethylene glycol formate, nano-sized sodium chloride and a polyvinyl alcohol-ethylene copolymer with a molecular weight of 5.0kDa are melt-blended to form a mixed system II, and then the mixed system I and the mixed system II are melt-blended , through the composite fiber spinning method, the polyester fiber of the sheath-core structure is prepared, and the skin layer in the polyester fiber of the sheath-core structure is a polyvinyl alcohol-ethylene copolymer layer containing sodium chloride, and the polyester fiber of the sheath-core structure _The core layer in is to contain ZrO Nano particle core layer;

2) Put the polyester fiber with a sheath-core structure prepared in step 1) into water for immersion and washing, and dissolve sodium chloride crystals to obtain a sheath-core fiber with several holes in the polyvinyl alcohol-ethylene copolymer skin layer, and the pore diameter is It is 40-50nm, the porosity is 50%, and the thickness of the polyvinyl alcohol-ethylene copolymer skin layer is about 13μm;

3) immersing the sheath-core fiber prepared in step 2) in a bromoisobutyryl bromide solution, and after reacting for 60 minutes, fully washing the fiber to obtain a fiber with atom transfer radical polymerization initiating activity;

4) The fiber with atom transfer radical polymerization initiating activity prepared in step 3) is immersed in a dimethylaminoethyl methacrylate solution containing cuprous bromide and bispyridine under a nitrogen protective atmosphere, and The molar ratio of cuprous bromide to dimethylaminoethyl methacrylate is 3:1, and the temperature is gradually raised to 80°C, and the reaction is kept for 16 hours to obtain poly(N,N-dimethylaminoethyl methacrylate) functionalized Polyester;

5) the polymethacrylic N, N-dimethylaminoethyl ester functionalized polyester fiber prepared in step 4) is mixed with polyethylene glycol under the catalysis of the phase transfer catalyst tetrabutylammonium bromide The potassium salt undergoes a nucleophilic substitution reaction to obtain a polyester fiber functionalized with poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate at the end.

6) Immerse the poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate functionalized polyester fiber with polyethylene glycol at the end prepared in step 5) in a divalent copper ion solution with a concentration of 0.45 mol/ml Complexation reaction occurred in the reaction for 2.0h, and the polyester fiber with antibacterial, deodorizing and health care functions was obtained.

The thickness of the polyvinyl alcohol-ethylene copolymer skin layer of the prepared polyester fiber is 13 μm, the pore diameter is 40-50 nm, and the porosity is 50%; the average diameter of the polyester core layer is 14 μm.

The above embodiments are only the best examples, rather than limiting the implementation of the present invention. In addition to the above-mentioned embodiments, the present invention also has other embodiments. All technical solutions formed by equivalent replacement or equivalent transformation fall within the scope of protection required by the present invention.

Claims (10)

1. a kind of polyester fiber with antibacterial deodorization health care function, it is characterized in that: this polyester fiber is skin-core structure, and polyester constitutes the core layer of skin-core structure, polyvinyl alcohol-ethylene copolymer is in core layer Periphery, enclosing the cortex that forms the skin-core structure; the polyvinyl alcohol-ethylene copolymer is connected with polydimethylaminoethyl methacrylate outward along the radial direction of the skin-core structure, and the polydimethylaminoethyl methacrylate Aminoethyl ester complexes with divalent copper ions to form an antibacterial layer of polyester fiber, and the end of polydimethylaminoethyl methacrylate is connected with polyethylene glycol to form a skin-friendly and hydrophilic layer on the surface of polyester fiber. 2. the polyester fiber with antibacterial and deodorant health care function according to claim 1, is characterized in that: the zirconium dioxide nano-particle is embedded in the polyester core layer of polyester fiber, and the quality of the zirconium dioxide nano-particle is 1.5-4.0% of the weight of the polyester core layer. 3. The polyester fiber with antibacterial, deodorant and health care functions according to claim 2, characterized in that: the average particle diameter of the zirconium dioxide nanoparticles is 30-60 nm. 4. The polyester fiber with antibacterial, deodorant and health care functions according to claim 1, 2 or 3, characterized in that: the thickness of the polyvinyl alcohol-ethylene copolymer cortex of the polyester fiber is 7-15 μm, and The skin layer of the polyvinyl alcohol-ethylene copolymer contains several holes with a diameter of 20-50nm and a porosity of 40-50%. 5. according to claim 1 or 2 or 3 described polyester fibers with antibacterial deodorant health care function, it is characterized in that: the polyester core layer of described polyester fibers is polyethylene terephthalate, and The average diameter of the polyester core layer is 14-20 μm. 6. according to claim 1 or 2 or 3 described polyester fiber with antibacterial deodorant health care function, it is characterized in that: described polydimethylaminoethyl methacrylate is complexed with divalent copper ion by coordination bond , and the molar ratio of dimethylaminoethyl methacrylate to divalent copper ions is 2 to 3:1. 7. The polyester fiber with antibacterial, deodorant and health care functions according to claim 1, 2 or 3, characterized in that: the polyethylene glycol has a molecular weight of 3.0 to 5.0 kDa, and the polydimethylmethacrylate The molecular weight of aminoethyl ester is 8.0-10.0kDa. 8. A method for preparing the polyester fiber according to any one of claims 1-7, characterized in that: comprising the steps of: ₁ ) ZrO Nanoparticles and polyethylene terephthalate are blended to form mixed system I, sodium chloride and polyvinyl alcohol-ethylene copolymer are blended to form mixed system II, then mixed system I and mixed system II melt blending, by sheath-core spinning method, the polyester fiber of sheath-core structure is prepared, and the cortex in the polyester fiber of sheath-core structure is the polyvinyl alcohol-ethylene copolymer layer that contains sodium chloride, sheath-core The core layer in the structured polyester fiber is a core layer containing zirconia nanoparticles, and the sodium chloride is sodium chloride with nanometer particle size; 2) placing the polyester fiber with a sheath-core structure prepared in step 1) into water for immersion, washing, and dissolving sodium chloride crystals to obtain a sheath-core fiber with several holes in the polyvinyl alcohol-ethylene copolymer skin layer; 3) immersing the sheath-core fiber prepared in step 2) in bromoisobutyryl bromide solution, a free radical activation reaction occurs, and the fiber is fully washed to obtain a fiber with atom transfer radical polymerization initiating activity; 4) The fiber with atom transfer radical polymerization initiating activity prepared in step 3) is immersed in a dimethylaminoethyl methacrylate solution containing cuprous bromide and bispyridine under a nitrogen protective atmosphere to generate Polymerization to obtain polyester fibers functionalized with N,N-dimethylaminoethyl methacrylate; 5) The poly(N,N-dimethylaminoethyl methacrylate) functionalized polyester fiber prepared in step 4) undergoes a nucleophilic substitution reaction with potassium salt of polyethylene glycol under the condition of a phase transfer catalyst, A polyester fiber functionalized with poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate at the end is obtained. 6) Immersing the polyester fiber functionalized with poly(ethylene glycol) N,N-dimethylaminoethyl methacrylate at the end prepared in step 5) in a divalent copper ion solution for a complex reaction to obtain Polyester fiber with antibacterial and deodorant health functions. 9. the preparation method of polyester fiber according to claim 8 is characterized in that: the reaction time in described step 3) is 30～60min, and the reaction condition in described step 4) is, be warming up to 65～60min gradually. 80°C, then keep warm for 16-20h. 10. according to the preparation method of claim 8 or 9 described polyester fibers, it is characterized in that: the phase transfer catalyst in the described step 5) is tetrabutyl ammonium bromide, the divalent copper in the described step 6) The concentration of the ion solution is 0.45-0.55 mol/ml, and the complexation reaction time is 1-2 hours.